Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/12—Esters of monohydric alcohols or phenols
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
  • C09D133/04—Homopolymers or copolymers of esters
  • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
  • C09D133/062—Copolymers with monomers not covered by C09D133/06
  • C09D133/064—Copolymers with monomers not covered by C09D133/06 containing anhydride, COOH or COOM groups, with M being metal or onium-cation
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof

Definitions

• Plasters bonded with synthetic resin are preferably produced with binders based on polymer dispersions.
• copolymer dispersions of acrylic and methacrylic acid esters are used which have a water absorption (determined according to DIN 53 495) of approx. 15 to 25% by weight.
• the plasters produced with these binders tend to chalk and in terms of fire behavior, they only just meet DIN 4102.
• copolymer dispersions made from acrylic acid esters and styrene which have a water absorption of approximately 15 to 20% by weight. The plasters produced with this do not meet the flammability test according to DIN 4102.
• Aqueous dispersions of copolymers of butadiene and styrene also meet less stringent requirements, but the plasters produced with them are less resistant to light, i.e. they yellow more easily, chalk very quickly (after one year) and become brittle. Therefore, they are not very common.
• Binders based on aqueous dispersions of vinyl esters are also used, but they are less weatherproof and less stable to saponification, especially if they contain vinyl acetate as the main monomer.
• the aqueous dispersions can be prepared in a customary manner by emulsion copolymerization of the monomers using the customary emulsifying and dispersing auxiliaries and the customary water-soluble, radical-forming polymerization initiators, such as alkali persulfates, advantageously in combination with water-soluble reducing agents such as formaldehyde sulfoxylate, thiosulfate or sodium pyrosulfite .
• the emulsifiers used are preferably alkylphenols and / or their sulfuric acid esters reacted with ethylene oxide in amounts of from 1 to 4, preferably from 1.5 to 2.5,% by weight, based on the monomers.
• Polymerization, in which the monomers can be added to the polymerization mixture on their own or in emulsified form can usually be carried out at temperatures from 30 to 90 ° C., preferably from 50 to 70 ° C.
• the amount of vinylidene chloride is preferably 20 to 40% by weight, based on the total monomers. It can be completely replaced by vinyl chloride.
• the amount of (meth) acrylic acid esters and optionally styrene, vinyl acetate or vinyl propionate is preferably 66 to 78% by weight, and acrylic and methacrylic acid esters of alkanols containing 1 to 4 carbon atoms are preferred, the corresponding acrylic acid esters being of particular interest.
• Suitable monomers (c) are, above all, acrylic acid, methacrylic acid, acrylamide and methacrylamide and also crotonic acid, itaconic acid, maleic acid, crotonic acid amide, itaconic acid mono- and diamide and maleic acid mono- and diamide. Their amount is preferably 2 to 4% by weight, based on the total monomers.
• the concentration of the aqueous vinylidene chloride copolymer dispersion can be varied within a wide range when used according to the invention. It is generally between 40 and 60% by weight, but can also be above or below.
• vinylidene chloride copolymer dispersions used as binders can also use other common additives in the production of the plasters, for example thickeners such as cullulose ether, polyacrylic acid derivatives or thickeners based on polyurethanes and film-forming aids such as mineral spirits, glycol ethers and esters, and the usual pigments such as rutile-type titanium dioxide and fillers based on calcite or talc be used.
• the plasters produced using the aqueous vinylidene chloride copolymer dispersions according to the invention are notable in particular for a particularly long open time and good processability. They also result in plasters of particularly high water resistance, which show no yellowing and which are flame-retardant according to DIN 4102.
• the water absorption according to DIN 53 495 is around 5 to 15%, so it is very important.
• the surprisingly high open time of the plasters has a particularly favorable effect when they are processed at higher temperatures, e.g. when the sun shines in summer.
• a copolymer of butyl acrylate and styrene was used as the binder, which is compared with a dispersion according to Example 2. Both dispersions have almost the same MFT.
• Both binders contained the same emulsifiers, auxiliaries, etc.
• Rub plaster the composition of which is given below, is applied to a non-absorbent surface. After application, the plaster is allowed to dry slightly. If the plaster is too soft, it cannot be structured. If it has reached a favorable consistency, the plaster is rubbed off with a trowel, whereby the desired rough structure is formed. This is only possible in a certain period of time. If you wait longer and then rub, the plaster comes off the wall.
• the rough plaster with the conventional binder could be rubbed with the trowel after about 20 minutes. After about 25 minutes the plaster had dried to the point where it could no longer be processed.
• Rubbing plaster with a binder according to Example 2 was smoother. The plaster could be rubbed with the trowel after about 12 minutes. It was only after about 30 minutes that he was tied.
• the drying rate of dispersion films is known to be determined by the rate of evaporation of water and not by the composition of the polymer (JW Vanderhoff, EB Bradford, WK Carrington in J. Polym. Sci., Symposium No 41 (1973) 155) .
• the low water absorption of the set plasters has a very advantageous effect by greatly reducing the undesired tarnishing, e.g. with plastering, off. Resistance to algae and moss growth is also valued.
• the binders claimed have a significantly improved abrasion resistance compared to the known binders.
• the abrasion resistance or wash resistance is tested according to DIN 53 778. In the known binders it is 1500 cycles, in the binders according to the invention it is 2000-2500 cycles with a PVC of 81%. The favorable properties are retained at VDC quantities above 50%, but the yellowing then increases, which is undesirable.
• a pressure-resistant polymerization vessel with a volume of 200 parts by volume, 31.66 parts of water, 0.18 parts of potassium persulfate and 0.18 parts of a 40% strength aqueous solution of the sodium salt of C15 paraffin sulfonate are initially introduced.
• the mixture is then flushed three times with 5 bar of nitrogen, depressurized and 9.5 parts by volume of feed I are added.
• the mixture is heated to 60 to 70 ° C. and, when 35 ° C. is reached, the feeds I and II are continuously added, which are added within 4 hours.
• the reaction mixture is then kept at 60 ° C. for 3 hours, flushed with nitrogen and then cooled and the pH is adjusted to 7-9 with ammonia.
• an aqueous emulsion of 12.17 parts water, 0.4 parts acrylamide, 0.6 parts acrylic acid, 12.06 parts vinylidene chloride, 25.14 parts n-butyl acrylate and 12.07 parts methyl methacrylate is emulsified with a mixture from 2.06 parts of a 35% aqueous solution of the sodium salt of the sulfuric acid ester of para-isooctylphenol ethoxylated with 25 mol of ethylene oxide and 1.26 parts of an aqueous 20% solution of para-isooctylphenol ethoxylated with 25 mol of ethylene oxide, as feed II, a solution of 0.09 parts of sodium formaldehyde sulfoxylate in 2.13 parts of water.
• the aqueous dispersion obtained has a solids content of 50.7%, its LD value is 81% and the minimum film-forming temperature (MFT) 6 ° C. (the LD value is the light transmittance as a percentage of an aqueous solution diluted to 0.01% by weight solids content) Dispersion).
• the polymerization is carried out as indicated for Example 1, but using a mixture of 1.8 parts of acrylamide, 1.2 parts of acrylic acid, 20.1 parts of vinylidene chloride and 27.2 parts of isobutyl acrylate as feed I.
• An aqueous dispersion with a solids content of 50.2% and an LD value of 86% is obtained under otherwise identical conditions.
• Your MFT is 15 ° C.
• a feed mixture I is a monomer mixture of 0.6 parts of acrylamide, 0.9 parts of acrylic acid, 5.03 parts of vinylidene chloride and 43.74 parts of methyl acrylate.
• An aqueous dispersion with a solids content of 50.5% is obtained, the LD value of which is 72% and the MFT of which is 13 ° C.
• the polymerization is carried out as indicated in Example 1, but using feed I made from 0.75 part of acrylamide, 0.75 part of acrylic acid, 10.06 parts of vinylidene chloride, 28.15 parts of n-butyl acrylate and 10.56 parts of styrene.
• An aqueous dispersion having a solids content of 51.2%, an LD value of 82% and an MFT of 4 ° C. is obtained.
• a feed mixture I is made from a monomer mixture of 0.8 part methacrylamide, 1.21 part methacrylic acid, 15.08 part vinylidene chloride and 33.18 part ethyl acrylate.
• a 48.9% aqueous polymer dispersion with an LD value of 91% and an MFT of 10 ° C. is obtained.
• the polymerization is carried out as indicated in Example 1, but a monomer mixture of 0.5 part of acrylamide, 0.75 part of acrylic acid, 12.07 parts of vinylidene chloride, 15.58 parts of tert-butyl acrylate and 21.37 parts of n-butyl acrylate is used as the feed.
• a polymer dispersion having a solids content of 52.2%, an LD value of 89% and an MFT of 4 ° C. is obtained.
• Polymerization is carried out as indicated in Example 1, but using a monomer mixture of 1 part of acrylamide, 1 part of methacrylic acid, 10.06 parts of vinylidene chloride, 5.03 of vinyl chloride and 33.18 parts of isobutyl acrylate as feed I.
• a polymer dispersion with a solids content of 49.2%, an LD value of 85% and an MFT of 4 ° C. is obtained.
• the polymerization is carried out as indicated in Example 1, but using a monomer mixture of 0.5 part of acrylamide, 1 part of acrylic acid, 25.15 parts of vinylidene chloride, 19.19 parts of vinyl propionate and 4.53 parts of butyl acrylate as feed I.
• a rubbing plaster is produced according to the recipes given below and tested as follows:
• the binder content is about 6.5%, the solids content about 86%, the specific weight about 1.9 g / cm3.
• Rubbing plasters with a thickness of about 50 ⁇ m (paints) or about 2.5 mm (plasters) were applied in the usual way to a primed, plastered outer wall, a stainless steel smoothing trowel (trowel) being used for the rubbing plaster.
• the rubbing plasters were weathered for 2 years. After the weathering, the plasters were practically not dirty and showed no cracks. In addition, the plastered areas were free from algae and moss growth.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Life Sciences & Earth Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Health & Medical Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Wood Science & Technology (AREA)
• Paints Or Removers (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Adhesives Or Adhesive Processes (AREA)

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• 1984
  • 1984-11-08 DE DE19843440792 patent/DE3440792A1/de not_active Withdrawn
• 1985
  • 1985-10-25 EP EP85113573A patent/EP0180868B2/de not_active Expired - Lifetime
  • 1985-10-25 AT AT85113573T patent/ATE71398T1/de active
  • 1985-10-25 DE DE8585113573T patent/DE3585138D1/de not_active Expired - Lifetime
  • 1985-11-01 US US06/793,831 patent/US4663384A/en not_active Expired - Fee Related
  • 1985-11-07 AU AU49453/85A patent/AU582396B2/en not_active Ceased
  • 1985-11-07 JP JP60248143A patent/JPS61166808A/ja active Granted
  • 1985-11-08 ES ES548721A patent/ES8704193A1/es not_active Expired

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